Manufacture of colored glass by addition of colorant to flint glass in a feeder



United States MANUFACT RE on COLORED GLASS BY. mm. TION F COLORANT T0 FLINT GLASS IN A FEEDER w 7 Basil D. Beck, Sr., Bridgeton, NJ., and Arthur B. Swain, Toledo, Ohio, assignors to Owens-Illinois Glass Company, a corporation of Ohio No Drawing. Application January '30, 1957 I Serial No'.' 637,098

1 Claim. (0.106 -52) The molten glass herein referred to 'as the ,base, glass flows from the tank through a forehearth fromfwhich it is withdrawn to form mold charges. In makingcolored glasses, the colorant materials'may be'added tothe clear or colorless base glass flowing through the 'foreh'earth. Such method, wherein the colorant material is added in the forehearth, permits a quick change from the clear glassto glass of the desired color and vice versa, which is impossible where the glass is colored by adding-the colorant material to the base glass batch or to the glass while in themelting tank.

'Moreover, in the manufacture of glasses of-certain colors as, for. example, a blue glassof the formula given hereinafter, adding the coloring materials .in' the rnain tank furnace operates to saturate. thetankswalls with the color material. As a result, it is impossible there.-

after to make clear glass within the furnace tank. The

absorption of the color materials by the furnace .tank walls is due to the high temperatures which prevail within the tank. On the other hand, the comparatively low temperatures required in the feeder 'forehearthobviate' the above condition of saturation 'or' absorbingfojf the colorant. Accordingly, clear and colored glasses may be made alternately without detrimental effects when the colorant is added within theforehearth. f

Colored glasses are importantin the glass industry as a good color improves the appearance of'the glass and of the articles or products put up in'glass containers and enhances their sale in .a competitive market. Various colors and shades of. color are produced; commercially and are known in the trade by various trade names as,

for example, Georgia green, Horseradish green, Rum

green, Emerald green, MilkBottle pink, .etc.

In developing such colored glasses by the above method in which the colorant is added withinthe'forehearth;

considerable difliculty has'been experienced'owing to the detrimental effect of the decolorizersused in'the base glass, which conflict with the colored batch materials added in the forehearth. During experimentation to def" velop satisfactory colorant feeder operation whereinva'rious colors are produced by the addition of highly en-jj riched colorant to a flint glass in the forehearth, we have encountered difficulty inrnaking a desired color or shade of color as, for example, the desired shade of Georgia- In such experimentation, the results]; of j green glass.

crucible melts .1n the laboratory and actual trial runs-in the field showed that this difficulty was chiefly due to' the fact that the decolorizers present in the flint glass had a detrimental effect on the brightness of the cjolor produced, and also due to the fact that 'the oxygen balance in the finished Georgia green glass was on the reducing side of neutral; We 'have'fiirther"discovered after considerable experimeh aidh that the foregoing difii-i culty could be overcome by the use of arsenic and'sodium nitrate in the highly enriched colorant. The use of these oxidizing; agents in the colorant added to the base glass 5 destroyed or counteracted the detrimental effect of the decolorizers in the base (flint) glass and also stabilized the oxygen balance of the color which is essential. to produce a bright Georgia green color.

In practicing our invention, the colorant added in the forehearth is usuallyin the form of a'frit. Examples of batch formulae for making the hits are given herein after.

The apparatus used in practicing the method in the present invention maybe any well known or approved apparatus comprising a melting tank for the clear glass with the forehearth intowhich the colorant is introduced and mixed with the "clear glass. An example of such anapparatus is disclosed in the copending application by Rough and Swain, Jr., Serial No. 578,632, filed April 17,

1956, Apparatus for Mixing Colorant in Glass Furnace .Forehcarth. I The oxidizing agents introduced into the frit batch not only. exert an oxidizing effect upon the ingredients of the frit batch. during its-melting in the forehearth, but

also exert an oxidizing effect upon ingredients such as' iron and selenium within. the molten base glass from the main tank whilewithin the colorant forehearth. The oxidation of iron changes it from blue-green to yellowishgreen thereby increasing'its light transmission or bright 80 ness. The oxidation of selenium produces a color change in themanner presently described. 'The sodium nitrate insures the oxidation of all the ferrous iron to ferric" iron. It also insures the complete oxidation of the arsenic in the frit batch. The arsenic in the frit batch oxidizes 85' the selenium; present. in the base (flint) glass and also stabilizes the oxygen balance 'ofthe chromium during the operation of the colorant in the forehearth.

The amount of .arsenicand sodium nitrate may vary to some extent. jWe have, found that very. satisfactory ,40 results are given by the use of 27 pounds of arsenic and 27 pounds of sodium nitrate per tonofsand in the frit "batch. The amounts of arsenic and sodium nitrate re.-.

quired to give the desired results depend to some extent on the composition of the base-glass. For example,

the amount of. arsenic and sodium nitrate can be reduced where the amount of selenium in the baseglass'is comparatively smalll Quantities from 12 pounds up to 60 pounds of arsenic and 12 pounds 'up to amaximum of 60 pounds of sodium nitrate per 'tonof' sand .;in the produces 'a red or reddish-brown color whereas the oxidized. 'elenium is colorless and in this latter case pro- "jfduces a 'glass of greater brightness. V

ferredto as normal flint glass contains 0.00025 to 00030% selenium remaining in the glass after the action fj of the decolon'zer used in the glass batch. The pink glass commonly used for making milk bottles, herein referred j to asfa Milk Bottle pink glass, carries a selenium content of 0.0003510 0.00055%. When a highly enriched color frit' is added to the normal flint glass or to the Milk Bottle pink glass the selenium present masks the color and lowers ta e b-2,1960.

frit batch may beused. The percentage of arsenic and. -.sodium nitrate in the finished frit should be within a f The oxidation of the selenium changes its light absorp A flint glass extensively used commercially and herein 3 the brightness to a point where it is not acceptable. We have found that 'a frit with 0.79% As O or As 'O will destroy or prevent the detrimental effect of the selenium present in the normal flint glass and thus produce a color which issatisfactory to the trade. If the base glass to which the color is added is a Milk Bottle pink additional niter and arsenic should be used in the frit. An amount of 0.79% arsenic in the frit is found to be a satisfactory percentage when a flint glass is employed as a base glass.

A general flint glass for the use in the manufacture of containers such as above mentioned is produced as near a colorless glass as it is'possible to produce within reasonable costs. A normal'light green color that would result from iron impurities in the raw batch materials is offset by complementary colors such as blue from cobalt and pink from selenium. This colorless glass does not transmit as :much total light as would be transmitted if cobalt and :selenium had been omitted. Accordingly when a highly colored glass frit is added to a decolorized flint glass so :as to produce, for example, a definite shade of green or with color characteristics within acceptable limits, the resultant glasslacks desired brightness. The use of oxidizing agents in the frit glass batch as above explained "increases the brightness of the color obtained where the colora nt glass frit has been added to a decolorized flint ,glass.

The base glass which is to be colored in the forehearth by the use of the glass frit may be a soda-lime flint or a boro-silicate glass.

The following table, Table I, gives a range of percent- :ages of the several constituents which may be used for base glass compositions adapted for use in the manufac- :ture of flint glassware such as bottles, jars, tumblers, and '-.various other articles.

TABLE I Range of oxides in base glass compositions, percent Base glass compositions coming within the ranges above given in Table I may be used with the various fritcompositions herein specified. These base glass compositions may have added thereto selenium as a decolorizer in an amount within the range of about 0.00025% to 0.00030%.

The following base glass batches numbered I and II respectively are soda-lime flint batches which we have successively colored by highly enriched colorant frit in accordance with the present invention.

Example I Example II Percent Percent 72.01 71. 45 1. 74 1. 32 .039 .037 .029 .013 11. 38 8.32 MgO 1.15 5. 58 I Alkalies 13.65 13.28 Selenium 0.00025 to 0.00025 to 0. 00030 0. 00030 Samples of frit batches for colorants which we have used with soda-lime flint base glasses given in the above Examples I and H are as follows:

Example III Georgia green frit batch:

Sand lbs 2000 Soda ash lbs 656 Hi cal limestone lbs 632 Sodium nitrate lbs 27 Arsenic lbs.. 27 Iron chromite lbs 118 Cobalt oxide oz 45 Theoretical: Percent CI'203 C0 0 .096 AS203 Example IV 30 Dark blue glass frit batch: Lbs. Sand V Soda ash 7 20 Burned lime 372 Nepheline syenite 208 Gypsum 24 Sodium nitrate 27 Arsenic 27' Cobalt oxide 164 40 Theoretical: I Percent C0 0 5.16 AS203 Example V Horseradish (blue green) frit batch: Lbs. Sand 2000 Soda ash 672 Burned lime 420 Sodium syenite' 176 Nitrate 27 Arsenic n '27 Copper oxide 200 The following examples numbered VI to X are samples I of frit glass ingredients of frits used in making Georgia Green glass. Each example gives the weight in pounds andounces of the ingredients for the frit batch and also the percentages of the various oxides comprised in the frit.

VI VII VIII IX X 2, 000 2, 000 2, 000 656 686 686 632 632 632 40 40 27 40 40 27 118 118 118 38 38 45 68. 93 68. 52 68. 88 78 77 77 1. 18 1. 17 1. 18 067 067 067 11. 81 I1. 74 11. 80 59 59 .015 015 015 13. 60 14. 12 14. 03 1. 78 1. 77 l. 78 081 081 096 1. 17 1. 16 79 2, 907. 37 2, 924. 77 2, 909. 41 .Dtol 21.9t01 1851201 The frit is added to the base glass flowing through the forehearth at a rate necessary to produce the desired amount of colorant in the base glass, but such rate obviously will vary with the particular shade or color desired. For example, in making a green glass, using the frit formula given in the above Example III, the frit will be added to the clear glass in a proportion to give 0.015% Cr O in the finished glass. As another example, in making dark-blue glass with the frit batch given in the above Example IV, the frit will be, added to the clear or base glass at a rate to give a percentage of 0.059 to 0.079% cobalt oxide in the finished glass, depending upon the shade of blue desired.

Modifications may be resorted to within the spirit and scope of our invention.

We claim:

In a method of making a colored glass composition, the steps of preparing a substantially colorless molten base glass having the following composition:

Selenium 0.00025-0.00030 and adding to said molten glass a highly colored frit prepared from the following ingredients in the following proportions:

Ingredients: Parts Sand 1 2000 Soda ash 656-720 CaO 354-420 Nepheline syenite 0-208 NaNO 12-60 As O 12-60 the colorant.

References Cited in the file of this patent UNITED STATES PATENTS 2,034,994 Sharp et al. Mar. 24, 1936 2,309,070 Austin et al. Ian. 19, 1943 I 2,508,070 Lyle May 16, 1950 2,699,399 Armistead Jan. 11, 1955 

